EP0832042B1 - Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique - Google Patents

Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique Download PDF

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Publication number
EP0832042B1
EP0832042B1 EP97903541A EP97903541A EP0832042B1 EP 0832042 B1 EP0832042 B1 EP 0832042B1 EP 97903541 A EP97903541 A EP 97903541A EP 97903541 A EP97903541 A EP 97903541A EP 0832042 B1 EP0832042 B1 EP 0832042B1
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EP
European Patent Office
Prior art keywords
solution
chromium
acidity
compounds
value
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97903541A
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German (de)
English (en)
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EP0832042A2 (fr
Inventor
Arend Schuurman
Johan Faber
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Koninklijke Philips NV
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Koninklijke Philips Electronics NV
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Priority to EP97903541A priority Critical patent/EP0832042B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H3/00—Electrochemical machining, i.e. removing metal by passing current between an electrode and a workpiece in the presence of an electrolyte
    • B23H3/10—Supply or regeneration of working media
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C02F1/64—Heavy metal compounds of iron or manganese
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Definitions

  • the invention relates to a method of removing iron compounds and chromium compounds from an aqueous electrolytic solution.
  • the invention also relates to the use of this method in reprocessing the electrolytic solution used in the electrochemical machining of chromium-steel objects.
  • aqueous electrolytic solution containing chromium compounds and iron compounds may be formed, for example, during the so-called electrochemical machining (ECM) of chromium-steel objects.
  • ECM electrochemical machining
  • chromium-steel objects are placed in a highly ionic solution which, for this purpose, preferably contains a considerable quantity of sodium nitrate.
  • the object to be machined serves as the anode and the electrode of the ECM apparatus serves as the cathode.
  • an electric current is passed between the anode and the cathode. Under these conditions, the electrode serves as a shaping tool.
  • the object which serves as the anode dissolves locally, thereby forming metal ions, for example, in the form of metal hydroxide(s), while hydrogen is developed at the surface of the electrode.
  • This machining method enables (patterns of) randomly shaped holes to be formed in the chromium-steel object in a relatively simple and accurate manner.
  • Cr(VI) ions of the solution used form a strong oxidation agent and are very toxic.
  • the toxicity of Cr(VI) is approximately 100 times that of Cr(III).
  • Dependent upon the pH of the solution, Cr(VI) is found as a chromate, hydrogen chromate, dichromate or polychromate. Also because of this toxicity, efforts are made to selectively separate these ions from the electrolytic solution used.
  • the known method has a number of important drawbacks.
  • One of these drawbacks is that the precipitate formed contains both iron hydroxide and chromium hydroxide. This is very undesirable in view of the aim to collect these hydroxides separately. The cost of separating this precipitate at a later stage is unacceptably high.
  • a further drawback of the known method is that the overall quantity of metal hydroxides is increased because a considerable quantity of Fe(II) compound is added to the solution to be treated. This too is very undesirable.
  • the invention more particularly aims at a method in which iron- and chromium-containing compounds are formed which can be separately removed from the aqueous solution.
  • the overall quantity of compounds to be separated should be as small as possible.
  • the invention particularly aims at a method in which the aqueous electrolytic solution is purified in such a way that it can be re-used. It should also be possible to combine the inventive method with the electrochemical machining of chromium-steel objects in a simple and inexpensive manner.
  • the method in accordance with the invention is based on the surprising finding that, dependent upon the pH-value of the aqueous solution, the hydrogen peroxide present in said solution can react with Cr ions in two ways. In the case of a high acidity (pH ⁇ 7) hydrogen peroxide may cause the Cr(III) present to oxidize to Cr(VI), whereas in the case of a low acidity (pH ⁇ 4) hydrogen peroxide may reduce the Cr(VI) present to Cr(III).
  • the aqueous electrolytic solution comprises mainly electrolyte (for example, sodium nitrate) and chromate. Subsequently, the solution is acidified to a pH-value below 4. Under these conditions, substantially all of the Cr(VI) present is reduced to Cr(III) under the influence of a small hydrogen-peroxide deficiency, which Cr(III) is available in the solution as a soluble salt. After the subsequent reduction of the acidity of the solution (pH ⁇ 7), this Cr(III) precipitates as chromium hydroxide. This is also separated from the aqueous electrolytic solution, for example by centrifuging. However, filtering off the chromium hydroxide proved to be simpler.
  • the precipitate of chromium hydroxide obtained appears to be substantially free of iron hydroxide. Any enclosed sodium nitrate is removed from the precipitate in a simple manner by washing with water. The remaining aqueous electrolytic solution is substantially free of Fe ions and Cr ions. This solution predominantly comprises only the original electrolyte as well as ions of the compounds which have been added to adjust the degree of acidity. In the method in accordance with the invention, the originally present Fe ions and Cr ions are separately separated from the aqueous electrolytic solution.
  • a preferred embodiment of the invention is characterized in that the acidity of the solution in step c) is adapted in such a manner that the solution obtains a pH ⁇ 2. If the pH value of the solution is smaller than 2, then substantially all of the Cr(VI) of the solution is present as a dichromate (Cr 2 O 7 2- ). The presence thereof in the solution can readily be checked spectrophotometrically. This makes it possible to check whether all Cr(VI) has been converted to the desirable Cr(III). In the case of a small residue of dichromate, the quantity thereof can be determined spectrophotometrically, whereafter the necessary quantity of hydrogen peroxide can be added to the solution to reduce this residue to Cr(III). In this manner, the quantity of the toxic Cr(VI) in the solution can thus be minimized, i.e. to several tenths of one ppm.
  • Another preferred embodiment of the method in accordance with the invention is characterized in that sodium nitrate is used as the electrolyte, the adaptation of the acidity in steps a) and d) takes place by means of sodium hydroxide, and the adaptation of the acidity in step c) takes place by means of nitric acid.
  • This measure provides the method with the important advantage that no ions which are foreign to the system are introduced into the solution.
  • the electrolytic solution can be re-used, if necessary after adaptation of the sodium-nitrate concentration.
  • a further preferred embodiment of the method in accordance with the invention is characterized in that the electrolyte concentration in the aqueous solution is kept constant by means of electrodialysis.
  • the use of electrodialysis during the implementation of the method in accordance with the invention has the important advantage that the aqueous electrolytic solution can be regenerated in a closed circuit.
  • this embodiment of the method in accordance with the invention can very suitably be used to subject chromium-steel objects to electrochemical machining.
  • Fig. 1 shows a flow chart of an embodiment of the method in accordance with the invention.
  • an aqueous electrolytic solution containing iron compounds and chromium compounds was used to electrochemically machine chromium-steel objects.
  • Such objects are made of an alloy which contains predominantly iron (approximately 87 at. %) and chromium (approximately 13 at. %).
  • the relevant solution had a pH value of 7 and contained predominantly sodium nitrate (3 mol/l).
  • the solution additionally contained trivalent iron in the form of Fe(III) hydroxide (34.1 mg/l), trivalent chromium in the form of Cr(III) hydroxide (0.8 mg/l) and hexavalent chromium in the form of chromate (5.7 mg/l).
  • the overall quantity of hydrogen peroxide to be added was determined by means of the overall quantity of Cr ions present in the solution as well as by the redox reactions to be brought about by said hydrogen peroxide.
  • the quantity of Cr(III) ions should first be oxidized to Cr(VI) and then reduced to Cr(III).
  • the quantity of Cr(VI) ions should be reduced to Cr(III) in a single step. If the overall quantity of both types of Cr ions is known, the quantity of hydrogen peroxide to be added to the solution can be calculated by means of simple redox equations.
  • the filtrate was acidified by means of nitric acid (HNO 3 ; 1 mol/l) until the solution had a pH value ⁇ 2.
  • HNO 3 nitric acid
  • the hydrogen peroxide present in the solution reduces all of the bichromate formed to Cr(III).
  • spectrophotometry it was determined whether the bichromate had indeed been converted. If a small residue of bichromate was still present in the solution, then the quantity thereof was determined. Subsequently, a corresponding quantity of hydrogen peroxide was added to the solution to convert this residue to the desired Cr(III).
  • the pH of the solution was brought to 7 by means of sodium hydroxide.
  • the Cr(III) formed precipitates as chromium hydroxide.
  • the precipitate was separated from the solution by means of "cross flow” microfiltration and subsequently washed with water to remove any sodium nitrate. Analysis of the precipitate showed that it consisted of substantially pure (> 95 wt.%) chromium hydroxide.
  • the quantity of enclosed iron hydroxide was less than 1 wt.%.
  • the solution thus treated did not contain "foreign" ions but predominantly Na ions and NO 3 ions.
  • the aqueous electrolytic solution can be used again after the Fe compounds and Cr compounds have been removed.
  • the filtrate of block 3, which is formed in said separating process, is subsequently acidified by nitric acid which is formed by electrodialysis (block 6) of a part of the main stream of the solution.
  • the solution obtains an acidity of pH ⁇ 4, as a result of which chromium reduction takes place, so that all of the Cr(VI) is converted to Cr(III) (block 4).
  • the acidity is adjusted to a pH value ⁇ 2, initially only bichromate is formed. The conversion thereof to Cr(III) can be observed well by means of a spectrophotometer. If necessary, a small quantity of hydrogen peroxide is added, at this stage of the process to reduce substantially all of the bichromate. An optimum adjustment enables the residual concentration of Cr(VI) to be reduced to less than 0.1 ppm.
  • the solution is basified by means of sodium hydroxide, which has also been obtained via electrodialysis (block 6).
  • the solution obtains an acidity of pH ⁇ 7.
  • Cr(III) precipitates as chromium hydroxide which is subsequently separated (block 5). Said separation preferably takes place by means of "cross flow” microfiltration.
  • the chromium hydroxide separated is washed with water to remove any sodium nitrate (block 8).
  • a part of the filtrate formed during separating chromium hydroxide is introduced into the electrodialysis apparatus (block 6).
  • Sodium nitrate present in this part of the filtrate is divided into a nitric acid stream and a sodium-hydroxide stream. This is used to acidify or basify the main stream at an earlier stage in the process.
  • the filtrate treated in the electrodialysis apparatus has a lower sodium-nitrate concentration than the ingoing filtrate. This outgoing filtrate is led to the main stream. Under ideal conditions, the sodium-nitrate concentration in the regenerated solution (at the end of the cycle) is equal to that of the solution used (at the beginning of the cycle).
  • the above-described method provides a simple manner of selectively removing chromium compounds and iron compounds from an aqueous electrolytic solution which preferably contains sodium nitrate.
  • the necessary redox reactions take place via oxidation and reduction of Cr ions by means of hydrogen peroxide.
  • the pH value is preferably adapted by means of sodium hydroxide and nitric acid, so that no ions which are foreign to the process are added to the solution.
  • the inventive process enables such a solution to be regenerated rapidly and efficiently.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

Cette invention se rapporte à un procédé pour éliminer les composés de fer et les composés de chrome qui sont présents dans une solution électrolytique aqueuse. Ce procédé se caractérise par la succession suivante d'étapes: a) ajouter du peroxyde d'hydrogène à la solution et, si nécessaire, adapter l'acidité de la solution, pour que la valeur du pH de la solution soit ≥ 7; b) séparer l'hydroxyde de fer qui s'est formé; c) adapter l'acidité de la solution, pour que la valeur du pH de la solution soit ∫ 4; d) adapter l'acidité de la solution pour que la valeur du pH de la solution soit ≥ 7; e) séparer l'hydroxyde de chrome qui s'est formé. Le procédé décrit ci-dessus offre une manière simple d'éliminer sélectivement les composés de chrome et les composés de fer présents dans une solution électrolytique aqueuse qui contient de préférence du nitrate de sodium. Les réactions redox nécessaires se produisent par oxydation et réduction des ions C au moyen de peroxyde d'hydrogène. La valeur du pH est adaptée au moyen d'hydroxyde de sodium et d'acide nitrique, pour qu'aucun ion qui serait étranger au procédé ne soit ajouté à la solution. Ce procédé permet de régénérer une telle solution.

Claims (5)

  1. Procédé pour éliminer les composés de fer et les composés de chrome présents dans une solution électrolytique aqueuse, lequel procédé comprend la succession suivante d'étapes:
    a) l'addition d'un excès de peroxyde d'hydrogène à base de la quantité de chrome présent à la solution et, au besoin, l'adaptation du degré d'acidité de la solution de façon que la valeur pH de la solution soit ≥ 7;
    b) la séparation de l'hydroxyde de fer formé;
    c) l'adaptation du degré d'acidité de la solution de façon que la valeur pH de la solution soit < 4;
    d) l'adaptation du degré d'acidité de la solution de façon que la valeur pH de la solution soit ≥ 7;
    e) la séparation de l'hydroxyde de chrome formé.
  2. Procédé selon la revendication 1, caractérisé en ce que le degré d'acidité de la solution dans l'étape c) est adapté de façon que la valeur pH de la solution soit < 2.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que du nitrate de sodium est utilisé comme l'électrolyte, l'adaptation du degré d'acidité dans les étapes a) et d) est effectuée à l'aide d'hydroxyde de sodium et l'adaptation du degré d'acidité dans l'étape c) est effectuée à l'aide d'acide nitrique.
  4. Procédé selon la revendication 3, caractérisé en ce que la concentration de l'électrolyte contenu dans la solution aqueuse est maintenue constante à l'aide d'électrodialyse.
  5. L'utilisation du procédé selon l'une des revendications précédentes pour retraiter une solution électrolytique utilisée dans l'usinage électrochimique d'objets en acier chromé.
EP97903541A 1996-03-27 1997-03-10 Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique Expired - Lifetime EP0832042B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97903541A EP0832042B1 (fr) 1996-03-27 1997-03-10 Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP96200831 1996-03-27
EP96200831 1996-03-27
PCT/IB1997/000212 WO1997035810A2 (fr) 1996-03-27 1997-03-10 Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique
EP97903541A EP0832042B1 (fr) 1996-03-27 1997-03-10 Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique

Publications (2)

Publication Number Publication Date
EP0832042A2 EP0832042A2 (fr) 1998-04-01
EP0832042B1 true EP0832042B1 (fr) 2001-09-26

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EP97903541A Expired - Lifetime EP0832042B1 (fr) 1996-03-27 1997-03-10 Procede pour eliminer les composes de fer et les composes de chrome presents dans une solution electrolytique aqueuse et utilisation de ce procede dans une operation d'usinage electrochimique

Country Status (5)

Country Link
US (1) US5783061A (fr)
EP (1) EP0832042B1 (fr)
JP (1) JP3998714B2 (fr)
DE (1) DE69706931T2 (fr)
WO (1) WO1997035810A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3686317A2 (fr) 2019-01-24 2020-07-29 MTU Aero Engines GmbH Procédé d'élimination des ions cr(vi) d'une solution aqueuse d'électrolytes

Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
DE69710044T2 (de) * 1996-09-13 2002-09-05 Koninklijke Philips Electronics N.V., Eindhoven Vorrichtung zum elektrochemischen bearbeiten von werkstücken
US6607651B2 (en) 1998-09-10 2003-08-19 Cws Parts Company Process and system for treating the discharge stream from an ion exchanger
CN1091426C (zh) * 1998-12-14 2002-09-25 华南理工大学 一种去除烧碱碱液中铁离子的方法
US20030209449A1 (en) * 2001-01-23 2003-11-13 Cws Parts Company Process and system for treating the discharge stream from an ion exchanger
DE10247318A1 (de) * 2002-10-10 2004-04-22 Robert Bosch Gmbh Verfahren zur Metallabreicherung in Nitratelektrolyten
DE102007044091A1 (de) * 2007-09-14 2009-03-19 Extrude Hone Gmbh Verfahren und Vorrichtung zur elektochemischen Bearbeitung
DE102007049495A1 (de) * 2007-09-14 2009-03-19 Extrude Hone Gmbh Vorrichtung und Verfahren zur elektrochemischen Bearbeitung
KR100916479B1 (ko) * 2007-11-30 2009-09-08 삼성전기주식회사 금속제품 전해가공용 전해액
US8936770B2 (en) * 2010-01-22 2015-01-20 Molycorp Minerals, Llc Hydrometallurgical process and method for recovering metals
ES2639025T3 (es) 2010-05-12 2017-10-25 Industria De Turbo Propulsores S.A. Método de obtención de electrolito reutilizable proveniente de maquinado electroquímico de partes hechas de níquel, hierro y cromo
DE102016004819A1 (de) 2016-04-21 2017-10-26 EMAG GmbH & Co. KG Verfahren zum Entfernen von Chromverbindungen aus Elektrolytlösungen
WO2025151163A1 (fr) * 2024-01-11 2025-07-17 Air Products And Chemicals, Inc. Appareil et procédé de purification de solution d'électrolyte pour la production d'hydrogène par l'intermédiaire d'une électrolyse

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US3896209A (en) * 1973-01-22 1975-07-22 Du Pont Reduction of hexavalent chromium
JPS51136362A (en) * 1975-05-21 1976-11-25 Mitsubishi Electric Corp Method of treating discharge sludge from electrolytic working into non polluting substance
US4321149A (en) * 1975-05-30 1982-03-23 Gte Products Corporation Process for removing multivalent metals from waste effluents
DE3542820A1 (de) * 1985-12-04 1987-06-11 Aeg Elotherm Gmbh Verfahren zur regeneration und entgiftung von elektrolyten der elektrochemischen metallbearbeitung
US5380441A (en) * 1993-09-15 1995-01-10 General Electric Company Removal of chromium from solution using mechanically agitated iron particles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3686317A2 (fr) 2019-01-24 2020-07-29 MTU Aero Engines GmbH Procédé d'élimination des ions cr(vi) d'une solution aqueuse d'électrolytes
DE102019200832A1 (de) 2019-01-24 2020-07-30 MTU Aero Engines AG VERFAHREN ZUM ENTFERNEN VON Cr(VI)-IONEN AUS EINER WÄSSRIGEN ELEKTROLYTLÖSUNG
US11389887B2 (en) 2019-01-24 2022-07-19 MTU Aero Engines AG Method of removing Cr(VI) ions from an aqueous electrolyte solution

Also Published As

Publication number Publication date
WO1997035810A2 (fr) 1997-10-02
JP3998714B2 (ja) 2007-10-31
DE69706931D1 (de) 2001-10-31
JPH11506052A (ja) 1999-06-02
US5783061A (en) 1998-07-21
EP0832042A2 (fr) 1998-04-01
DE69706931T2 (de) 2002-04-04
WO1997035810A3 (fr) 1997-11-06

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